Method of dyeing and product



Patented May 30, 1933 UNITED STATES PATENT oFFrc-s DONALD POWERS, OF PROVIDENCE, RHODE ISLAND, ASSIGNOR TO UNITED STATES FINISHING COMPANY, OF NEW YORK, N. Y., A CORPORATION OF CONNECTICUT I METHOD OF DYEING AND PRODUCT No Drawing.

This invention relates to an improved method of treating and dyeing articles, as well as an improved product derived by the practice of such method. This invention particularly relates to an improved method oftreating and dyeing articles comprised of -cellulose-acetate silk, which is sometimes-known as Celanese or Acele It is well appreciated that this product, known by those skilled in the art cellulose-acetate, has many advantages over other synthetic or natural fibers, but one of the greatest difficulties heretofore encountered has been in connection with the dyeing-and printing. of yarns and fabrics composed thereof. i

More particularly, while. during recent :years" it has become practicable to dye yarns of this character, or yarns of this character practice to dye the entire material body and thereupon to employ What has been known as a discharge agent, which destroyed or removed the color at its point of contact with the material.- It was also possible, if desired, to simultaneously dye or color the discharged area with a contrasting shade by the incorporation of'a dye or color with the discharging agent. This process is commonly known as color discharge printing and willbe referrcdto as such.

Thus, it is an object of the present invenmeans of which designs in contrasting colors may be incorporated 1n cellulose-acetatematerials to prodl lce the product of the present invention, such method being capable of practice at relatively smallexpense and with facility so that a commercially prac;

ticable method is tuught and an*article.-is

produced whidrn' ay be sold ata relatively nominal figure.

It is a further object of the invention to furnish a method and product in which per- Application filed novemberfaa, 1929. ser al No. 409,422..

fect designs will be achieved readily by 0perators' possessing merely ordinary skill. The following specification is to be regarded as illustrative and not in a limited sense. The scope of the invention will be apparent from a perusal of the claims; f

. In endeavoring to properly dye'acylated products of. cellulose such as cellulose formate, cellulose acetate or cellulose benzylate, penetrating or swelling agents such as for-.

mic acid, acetic acid, ethyl alcohol, acetone -or diacetone alcohol, 'phenol, resorcinol,

urea, ammonium sulphocyanide, and lactic acid have been employed. The resultant swelling of the fibers (as disclosed in Brit'- ish Patent 285,948, to Henry Dreyfus, granted August 10, 1927,) assists materially -1n penetrating the fibers with mordanting agents. As is Well known, these mordanting agents act to give body and weight to the material and may be, for example, inorganic-salts such as ferric chloride or tin chloride. .i

- However, while-these swellingor penetrating, agents are effective in dyeing or assisting in mordanting,they have not been printing of acylatedcellulose fabrics. T e usual method ofdischarge printing on fabrics containing acylated cellulose is to treat the fiber with the sulfoxylate of sodium formeffective in assistingthe color dischar e' aldehyde ('i. e., the formaldehyde reaction product with sodium sulfoxylate) or the sul .foxylate of potassium formaldehyde. This material destroys the color and leaves a white or contrasted shade where it has come in' contact with the. fabric. However, in the "l td"lll"f' tion to provide a method 'or; process byof my a 6 u 086 abncs the use of the sulfoxy late of sodium formaldehyde,

even in the presence 7 of penetrating and,

swelling agents, has caused unsatisfactory results,'-particularly if the material was dyed in a dark shade. It has been found thatwhile these penetrating agents do assis t in eflte'cting -a discharge. by themselves that unless the ground color can be successfully discharged, it is of little value to mix other colors with the discharge agent in an effort to obtain contrasting colors in the dischar ed area.

It as recently been found that a discharge on dyed cellulose-acetate fabrics may be obtained by use of the sulfoxylate of zinc formaldehyde. However, this product has, the limitation that itcannot be used in conjunction with fast colors to produce contrastin color effects, but can only be used to pro uce a white discharge or a fugitive color dischar e on cellulose-acetate fibers. To one skillefinthe art it is clear that discharge work where only white contrasting effects and fugitive color effects may be obtained is far more limited in its application than a discharge where both fast color and white effects may be obtained.

However, the use of organic derivatives of the sulfoxylate of sodium formaldehyde have been found to overcome these difiiculties and to give entirely satisfactory results. Where organic derivatives of'the sulfoxylate of sodium formaldehyde have been prepared, these organic sulfoxylates have been found to penetrate the fiber much more effectively than the sulfoxylate of sodium formaldehyde and give discharge patterns. The results obtained with the organic sulfoxylate alone were not entirely satisfactory, particularly' on the dark shades, but experiments made, using as a discharge agent a mixture of these" organic derivatives of the sulfoxylate of sodium or potassium formaldehyde, and a penetrating agent such as 'glycolic acid, gave perfect and complete discharge. These organic sulfoxylates have the advantage that they not only give a satisfactory white, similar to the sulfoxylate of zinc formaldehyde, but they may be mix'ed with fast colors of all types without any decomposition. I

Suitable organic derivatives of the sulfoxylate of sodium formaldehyde to act as discharge agents are preferably aliphatic or aromatic amine derivatives. Those of particular interest are: the aniline derivative,

the alphanaphthylamine derivative, the

para-amido-phenol derivative, the diphenylamine derivative, the paraphenylenediamine derivative, the orthotoluidine derivative, the xylidinederivative and the butylamine derivative. The organic derivatives of the sulfoxylate which are particularly effective are the reaction products of primary amines con- I densed with the sulfoxylate of sodium or potassium formaldehyde, with or without the elimination of water. For example:

It is understood that I do not wish to be limited to these specific compounds mentioned for it is obvious to one skilled in the art that many other organic compounds could be prepared with similar activity. It is also understood that I do not wish to be limited to the exact formula given in the equation. It should be pointed out that when organic compounds of the type given above are heated with the sulfoxylate of sodium or potassium formaldehyde that a reaction takes place liberating a large amount of heat. The resultant product is what I consider the organic sulfoxylate.

Now, dealing with the application of vat colors, it is known that while acetate cellulose products have been discharged with the aid of sulfoxylate of zinc formaldehyde (the formaldehyde reaction product with zinc sulfoxylate), resulting in a pattern embracing a field of any desired color with a white design, the sulfoxylate of zinc formaldehyde can not be used in conjunction with Vat colors. sulfoxylate of zinc formaldehyde can, however,be used with basic or direct colors. The latter colors have the disadvantage of not being fast to light, rubbing or washing. As a consequence, while it is thus possible to get colored discharges, it is obvious that the resultant product is of limited practical value. The reason that no practical results are obtained when vat colors are mixed with sulfoxylate of zinc fornraldehyde is that decomposition, or degradation of the latter compound may take place.

However, when I utilize vat colors in c011- junction with the organic sulfoxylate, anydesired colored discharge may be obtained which will not be fugitive nor will it be affected bylight or rubbing.

By vat colors are meant the broad class of fast colors whichare technically known as anthraquinone coloring matters and indigoid coloring matters. These classes of coloring matters have been commonly called vat colors by virtue of the common practice of applying them in a reducing vat.

An example of the present invention is as follows: If I employ a cellulose acetate fabric, and dye this a solid shade by padding through a solution of dianisidine and then developing with nitrite and beta-oxynaphthaic acid, I will have a fabric of deep blue color. This fabric may be properly discharged, for example, by printing with the following paste 60 parts dextrine 15 parts soda ash 10 parts potassium sulphocyanide 20 parts of the condensation product of aniline and the sulfoxylate of sodium formaldehyde 10 parts Indanthrene Golden orange G Paste (Colour Index #1096) This mixture is heated to approximately 140 degrees F. until it becomes uniform. The

paste is then printed' on the fabric dried. Subsequently, the fabric is subjected to the action of a vat ager, oxidized and washed in the usual fashion. The resultant product will be found to incorporate con trasting colors having clear lines of'demarcation and of the desired values, known as' vat discharge prints. I

Other. examples of the invention may include the substitution of acetone,urea, naphthol or resorcinol in place of potassium sulphocyanide as a penetrant. Further examples may substitute the alphanaphthy'lamine derivative, the butylamine derivative, the xylidine derivative, the ortho-toluidine derivative or the paratoluidine derivative in lieu of the aniline derivativeof the sulfoxylate of sodium formaldehyde used in the original example. further examples of the invention are to be found in substituting Ciba blue B (Colour Index No. 11 83), Alizanthene violet R (Col-' our Index No.1103), Ponsol blue GD (Colour Index No. 11-13) v or Algol scarlet G (Colour Index No. 1129) for the Indantiliirgne Golden orange G paste as afore spec-- 1 e Another example of the present "invention is asfollows. fabric has been dyed in a solid shade, -it may be properly discharged, by screen or film It is understood that this processnot only applies to fabrics which consist solely of acylated cellulose fibers, but may be applied with equal effectiveness and value to fabrics which contain mixtures of cellulose-acetate and other synthetic or natural fibers such as real silk, cotton or rayon.

It will thus be seen that a method is provided by means of which vat color discharges may be utilized in conjunction with acetate cellulose fabrics with the aid of penetrating agents and organic sulfoxylates.

This latter is to be interpreted sufficiently generically to include the reaction products of an organic amine with sulfoxylate. This process, moreover, permits the simultaneous discharging and vprlnting of an acylated cellulose fabric'with vat dyestufi'. c

From the foregoing, it will be understood that, among others, the objects of the invention as specifically afore stated are achieved. It will, moreover, be appreciated A that numerous changes in' the steps of the method and the appearance of the finished fabric might be resorted to without. in the a sulfoxylate. Still After the cellulose-acetate slightest departing from the spirit of invention as defined by. the claims.

the I Having thus described my invention, what I. claim asnew and desire to secure by Letters Patent.is: 7

,;1. A method of dyeing in contrasting colors a fabric of the V acylated cellulose group which includes dyeing said fabric and v applying thereto an agent embodying a vat dye, and including in said agent an aniline derivative of a formaldehyde sulfoxylate.

"2. A method 'of dyeing in contrasting colors a fabric of the acylated cellulose group which includesdyeing said fabric and applying thereto an agent embodying a vat dye, and including in said agent a reaction product of primary aminescondensed with 3. A method. of dyeing colors a fabric of the acylated cellulose group. which includes dyeing said fabric and applying thereto an agent embodying- 'a-v'at dye, and including in said agent the reaction product of an aromatic amine condensed'with a sulfoxylate. v

in contrasting 4. A method of dyelng 1n contrasting colors a fabric of the acylated cellulose group which includes dyeing said fabric and applying thereto an agent embodying a' vat dye and including in said agent a reaction product of primary amines condensed w th salts of sulfoxylate;

5. A. method, of colors a fabric of the acylated cellulose groupwhich includes dyeing said fabric and applying thereto an agent embodying a vat dye, and including in said agent a reaction .product of primary amines condensed with E sulfoxylateof sodium formaldehyde.-

'6. A method of 7 colors a fabric of the acylated cellulose group which includes dyeing said fabric and applying thereto an agent embodying a vat .dye, and including in said agent an aniline derivdying in contrasting K the formaldehyde derivatives of'the alkali dyeing in contrasting ative of the sulfoxylate of sodium formalde;

hyde. 7 A method of dyeing in contrastlng colors a fabric of the acylated cellulose group ing thereto an agent embodying a vat'dye; and including in said agent an amine derlvative of the sulfoxylate of sodium formaldehyde.

8. A method of dyeing incontrasting colors a fabric of the acylated cellulose group which includes dyeing said fabric and applying thereto an agent embodying a vat dye,

and including in said-agent-an aromaticv amine derivative of the sulfoxylate of sodium formaldehyde.

9. A method of dyeing incontrasting colors'a fabric of the acylated cellulose group which includes dyeing said fabric and apply ing thereto an agent embodying a vat dye,

which includes dyeing said fabric and apply-.

and including in said agent an aniline derivative of the sulfoxylate of sodium formaldehyde.

10. A method of dyeing in contrasting co1- ors fabrics of the acylated cellulose groups which includes initially dyeing said fabric and applying thereto a mixture comprising substantially 60 parts of a thickening agent, 15 parts soda ash, 10 parts of a penetrating agent, 20 parts of the condensation product of aniline and the sulfoxylate of sodium formaldehyde, '10 parts vat color.

- 11. A method. of dyeing in contrasting colors fabrics of the aoylated cellulose groups which includes initially dyeing said fabric and applying thereto a mixture comprising substantially 60 parts dextrine, 15 parts soda ash, 10 .parts potassiums'filpha cyanide, 20 parts of the condensation product of aniline and the sulfoxylate of sodium formaldehyde 10 parts vat color.

. 12. A method of dyeing in contrasting colors a fabric of the acylate-d cellulose type which includes dyeing said fabric with an initial color, and applying thereto a penetrating agent and an aniline derivative of a formaldehyde sulfoxylate to discharge said fabric, and simultaneously applying to the discharged portions of said fabric anthra quinone and or indigoid vat dyes.

13. A substance to be utilized in connection with the treatment of fibrous materials comprising a hydroxy-ethyl-amine derivative of the sulfoxylate of sodium formaldehyde, combined with a vat dye.

In testimony whereof I aflix my signature.

DONALD H. POWERS. 

